Liquid detergent compositions comprising quaternary nitrogen-containing and/or zwitterionic polymeric suds enhancers

ABSTRACT

Liquid detergent compositions comprising a polymeric material which is a suds enhancer and a suds volume extender, said compositions having increased effectiveness for preventing re-deposition of grease during hand washing are provided. The polymeric material which are suitable as suds volume and suds endurance enhancers comprise an effective amount of a quaternary nitrogen-containing monomeric unit and/or zwitterionic monomeric unit-containing polymeric suds enhancer comprise:  
     i) units capable of having a cationic charge at a pH of from about 4 to about 12; provided that said suds enhancer has an average cationic charge density of 2.8 or less units per 100 daltons molecular weight at a pH of from about 4 to about 12;  
     b) an effective amount of a detersive surfactant; and  
     c) the balance carriers and other adjunct ingredients;  
     provided that a 10% aqueous solution of said detergent composition has a pH of from about 4 to about 12.

RELATED APPLICATIONS

[0001] This application claims priority under 35 U.S.C. §119(e) to U.S.Provisional Application No. 60/259,962, filed Jan. 5, 2001.

FIELD OF THE INVENTION

[0002] The present invention relates to liquid detergent compositionssuitable for hand dishwashing comprising a polymeric suds volume andsuds duration enhancer wherein the polymeric suds volume and sudsduration enhancer comprises one or more quaternary nitrogen-containingmonomeric units and/or zwitterionic monomeric units. The polymeric sudsenhancers (suds boosters) suitable for use in the compositions of thepresent invention comprise have an average cationic charge density of2.8 or less, preferably from about 0.01 to about 2.8, more preferablyfrom about 0.1 to about 2.75, most preferably from about 0.75 to about2.25 units per 100 daltons molecular weight at a pH of from about 4 toabout 12. The present invention further relates to methods for providingenhanced suds volume and suds duration during hand washing.

BACKGROUND OF THE INVENTION

[0003] Liquid detergent compositions which are suitable for handdishwashing must satisfy several criteria in order to be effective.These compositions must be effective in cutting grease and greasy foodmaterial and once removed, must keep the greasy material fromre-depositing on the dishware.

[0004] The presence of suds in a hand dishwashing operation has longbeen used as a signal that the detergent continues to be effective.However, depending upon the circumstances, the presence of suds or thelack thereof, has no bearing upon the efficacy of liquid detergents.Therefore, the consumer has come to rely upon a somewhat erroneoussignal, the lack or absence of soap suds, to indicate the need foradditional detergent. In many instances the consumer is adding anadditional amount of detergent far in excess of the amount necessary tothoroughly clean the dishes. This wasteful use of detergent isespecially true in hand dishwashing since the soiled cooking articlesare usually cleaned in a “washing difficulty” queue, for example,glasses and cups, which usually do not contact greasy food, are washedfirst, followed by plates and flatware, and finally pots and pans whichcontain the most residual food material and are usually, therefore, the“greasiest”.

[0005] The lack of suds in the dishwater when pots and pans are usuallycleaned, together with the visual inspection of the amount of residualfood material on the cookware surface, typically compels the consumer toadd additional detergent when a sufficient amount still remains insolution to effectively remove the soil and grease from the dishware orcookware surface. However, effective grease cutting materials do notnecessarily produce a substantial amount of corresponding suds.

[0006] Accordingly, there remains a need in the art for liquiddishwashing detergents useful for hand washing dishware which have anenduring suds level while maintaining effective grease cuttingproperties. The need exists for a composition which can maintain a highlevel of suds as long as the dishwashing composition is effective.Indeed, there is a long felt need to provide a hand dishwashingcomposition which can be use efficiently by the consumer such that theconsumer uses only the necessary amount of detergent to fully accomplishthe cleaning task.

SUMMARY OF THE INVENTION

[0007] The present invention meets the aforementioned needs in that ithas been surprisingly discovered that polymeric materials comprising oneor more quaternary nitrogen-containing monomeric units and/orzwitterionic monomeric units have the capacity to provide liquid handwash detergent compositions with extended suds volume and suds durationbenefits. In other words, such polymeric materials are polymeric sudsenhancers (suds boosters).

[0008] In one aspect of the present invention, liquid detergentcompositions having increased suds volume and suds retention suitablefor use in hand dishwashing, said compositions comprising:

[0009] a) an effective amount of polymeric suds enhancer (suds booster)wherein the polymeric suds enhancer comprises one or more quaternarynitrogen-containing monomeric units and/or zwitterionic monomeric units,preferably wherein said stabilizer comprises:

[0010] i) units capable of having a cationic charge at a pH of fromabout 4 to about 12; provided that said suds enhancer has an averagecationic charge density of 2.8 or less, preferably from about 0.01 toabout 2.8, more preferably from about 0.1 to about 2.75, most preferablyfrom about 0.75 to about 2.25 units per 100 daltons molecular weight ata pH of from about 4 to about 12;

[0011] b) an effective amount of a detersive surfactant; and

[0012] c) the balance carriers and other adjunct ingredients;

[0013] provided that a 10% aqueous solution of said detergentcomposition has a pH of from about 4 to about 12, is provided.

[0014] In another aspect of the present invention, liquid detergentcompositions having increased suds volume and suds retention suitablefor use in hand dishwashing, said compositions comprising:

[0015] a) an effective amount of polymeric suds enhancer (suds booster)wherein the polymeric suds enhancer comprises one or more quaternarynitrogen-containing monomeric units and/or zwitterionic monomeric units,preferably wherein said stabilizer comprises:

[0016] i) one or more units capable of having a cationic charge at a pHof from about 4 to about 12; and

[0017] ii) one or more units having one or more hydroxyl groups;provided that said suds enhancer has a hydroxyl group density of about0.5 or less, preferably from about 0.0001 to about 0.4; and

[0018] iii) optionally, one or more other monomeric units describedhereinafter; provided that said suds enhancer has an average cationiccharge density of 2.8 or less; and

[0019] b) an effective amount of a detersive surfactant; and

[0020] c) the balance carriers and other adjunct ingredients;

[0021] provided that a 10% aqueous solution of said detergentcomposition has a pH of from about 4 to about 12, is provided.

[0022] In yet another aspect of the present invention, liquid detergentcompositions having increased suds volume and suds retention suitablefor use in hand dishwashing, said compositions comprising:

[0023] a) an effective amount of polymeric suds enhancer (suds booster)wherein the polymeric suds enhancer comprises one or more quaternarynitrogen-containing monomeric units and/or zwitterionic monomeric units,preferably wherein said stabilizer comprises:

[0024] i) one or more units capable of having a cationic charge at a pHof from about 4 to about 12; and

[0025] ii) one or more units having one or more hydrophobic groups,preferably the hydrophobic groups are selected from the group consistingof non-hydroxyl groups, non-cationic groups, non-anionic groups,non-carbonyl groups, and/or non-H-bonding group, more preferably thehydrophobic groups are selected from the group consisting of alkyls,cycloalkyls, aryls, alkaryls, aralkyls and mixtures thereof;

[0026] iii) optionally, one or more other monomeric units describedhereinafter; provided that said suds enhancer has an average cationiccharge density of 2.8 or less;

[0027] b) an effective amount of a detersive surfactant; and

[0028] c) the balance carriers and other adjunct ingredients;

[0029] provided that a 10% aqueous solution of said detergentcomposition has a pH of from about 4 to about 12, is provided.

[0030] In still another aspect of the present invention, methods forproviding increased suds retention and suds volume when hand washingdishware is provided.

[0031] These and other objects, features and advantages will becomeapparent to those of ordinary skill in the art from a reading of thefollowing detailed description and the appended claims.

[0032] All percentages, ratios and proportions herein are by weight,unless otherwise specified. All temperatures are in degrees Celsius (°C.) unless otherwise specified. All documents cited are in relevantpart, incorporated herein by reference.

[0033] Additional background on these compositions and methods isprovided by PCT Patent Application Serial Nos. PCT/US98/24853,PCT/US98/24707, PCT/US98/24699 and/or PCT/US98/24852 all incorporatedherein by reference in their entirety.

[0034] All substituent groups in structural formulas in theSpecification and Claims have the meaning defined in previous structuralformulas in the Specification or Claims, respectively, unless indicatedotherwise.

DETAILED DESCRIPTION OF THE INVENTION

[0035] Definitions

[0036] “Polymeric suds enhancers (suds boosters)”—“Polymeric sudsenhancers (suds boosters)” as used herein means polymeric materialscomprising one or more quaternary nitrogen-containing monomeric unitswhich are cationic monomeric units and/or zwitterionic monomeric units.The different types of polymeric materials which fall within thisdefinition are set forth below:

[0037] 1) polymeric materials comprising cationic monomeric units (i.e.,quaternary nitrogen-containing monomeric units alone or in combinationwith other cationic monomeric units);

[0038] 2) polymeric materials comprising cationic and nonionic monomericunits (i.e., quaternary nitrogen-containing monomeric units alone or incombination with other cationic monomeric units, plus one or morenonionic monomeric units);

[0039] 3) polymeric materials comprising cationic and anionic monomericunits (i.e., quaternary nitrogen-containing monomeric units alone or incombination with other cationic monomeric units, plus one or moreanionic monomeric units);

[0040] 4) polymeric materials comprising cationic, nonionic and anionicmonomeric units (i.e., quaternary nitrogen-containing monomeric unitsalone or in combination with other cationic monomeric units, plus one ormore nonionic monomeric units and one or more anionic monomeric units);

[0041] 5) polymeric materials comprising zwitterionic monomeric units(i.e., zwitterionic monomeric units alone);

[0042] 6) polymeric materials comprising zwitterionic and cationicmonomeric units (i.e., zwitterionic monomeric units, plus one or morecationic monomeric units);

[0043] 7) polymeric materials comprising zwitterionic and nonionicmonomeric units (i.e., zwitterionic monomeric units, plus one or morenonionic monomeric units);

[0044] 8) polymeric materials comprising zwitterionic and anionicmonomeric units (i.e., zwitterionic monomeric units, plus one or moreanionic monomeric units);

[0045] 9) polymeric materials comprising zwitterionic, cationic andnonionic monomeric units (i.e., zwitterionic monomeric units, plus oneor more cationic monomeric units and one or more nonionic monomericunits);

[0046] 10) polymeric materials comprising zwitterionic, cationic andanionic monomeric units (i.e., zwitterionic monomeric units, plus one ormore cationic monomeric units and one or more anionic monomeric units);

[0047] 11) polymeric materials comprising zwitterionic, nonionic andanionic monomeric units (i.e., zwitterionic monomeric units, plus one ormore nonionic monomeric units and one or more anionic monomeric units);

[0048] 12) polymeric materials comprising zwitterionic, cationic,nonionic and anionic monomeric units (i.e., zwitterionic monomericunits, plus one or more cationic monomeric units, one or more nonionicmonomeric units and one or more anionic monomeric units).

[0049] “Effective amount of a polymeric suds enhancer (suds booster)”—An“effective amount of a polymeric suds enhancer (suds booster)” as usedherein means a sufficient amount of the polymeric suds enhancer suchthat greasy and/or composite soils are removed and/or reduced from asubstrate coming into contact with the polymeric suds enhancer.

[0050] The present invention relates to polymeric materials whichprovide enhanced suds duration and enhanced suds volume when formulatedinto liquid detergent compositions suitable for hand dishwashing. Thepolymeric material comprises one or more quaternary nitrogen-containingmonomeric units and/or zwitterionic monomeric units, preferably whereinsaid polymeric material comprises an average cationic charge density of2.8 or less, preferably from about 0.01 to about 2.8, more preferablyfrom about 0.1 to about 2.75, most preferably from about 0.75 to about2.25 units per 100 daltons molecular weight at a pH of from about 4 toabout 12.

[0051] The liquid detergent compositions of the present inventioncomprise:

[0052] a) an effective amount of polymeric suds enhancer (suds booster)wherein the polymeric suds enhancer comprises one or more quaternarynitrogen-containing monomeric units and/or zwitterionic monomeric units,preferably wherein said stabilizer comprises:

[0053] 1) units capable of having a cationic charge at a pH of fromabout 4 to about 12;

[0054] provided that said suds enhancer has an average cationic chargedensity preferably from about 0.01 to about 2.8, more preferably fromabout 0.1 to about 2.75, most preferably from about 0.75 to about 2.25units per 100 daltons molecular weight at a pH of from about 4 to about12;

[0055] b) an effective amount of a detersive surfactant; and

[0056] c) the balance carriers and other adjunct ingredients;

[0057] provided that a 10% aqueous solution of said detergentcomposition has a pH of from about 4 to about 12.

[0058] It is preferred that the polymeric suds enhancer (a) preferablyfurther comprises one or more of the following:

[0059] ii) one or more units having one or more hydroxyl groups,provided that the polymeric suds enhancer has a hydroxyl group densityof about 0.5 or less, preferably from about 0.0001 to about 0.4 asmeasured by the Hydroxyl Group Density Equation as outlined in greaterdetail below; and/or

[0060] iii) one or more units having one or more hydrophobic groups,preferably the hydrophobic groups are selected from the group consistingof non-hydroxyl groups, non-cationic groups, non-anionic groups,non-carbonyl groups, and/or non-H-bonding group, more preferably thehydrophobic groups are selected from the group consisting of alkyls,cycloalkyls, aryls, alkaryls, aralkyls and mixtures thereof.

[0061] It is desirable that the polymeric suds enhancer (a) furtheroptionally, but preferably comprises one or more of the following:

[0062] iv) units capable of having an anionic charge at a pH of fromabout 4 to about 12;

[0063] v) units capable of having an anionic charge and a cationiccharge at a pH of from about 4 to about 12;

[0064] vi) units having no charge at a pH of from about 4 to about 12;and

[0065] vii) mixtures of units (iv), (v), (vi), and (vii).

[0066] The following describe non-limiting examples of polymericmaterial which may be suitable for use in the liquid detergentcompositions of the present invention.

[0067] Polymeric Suds Enhancers (Suds Boosters)

[0068] The polymeric suds enhancers of the present invention arepolymers which contain one or more quaternary nitrogen-containingmonomeric units and/or zwitterionic monomeric units, and preferablyfurther contain units capable of having a cationic charge at a pH offrom about 4 to about 12, provided that the suds enhancer has an averagecationic charge density of 2.8 or less, preferably from about 0.01 toabout 2.8, more preferably from about 0.1 to about 2.75, most preferablyfrom about 0.75 to about 2.25 units per 100 daltons molecular weight ata pH of from about 4 to about 12.

[0069] Preferably, the polymeric suds enhancers also include unitscapable of influencing the average cationic charge density of thequaternary nitrogen-containing or zwitterionic polymeric suds enhancers,preferably by decreasing the average cationic charge density of thequaternary nitrogen-containing or zwitterionic polymeric suds enhancers.Such units capable of influencing the average cationic charge density ofthe polymeric suds enhancers may, and preferably do, provide additionaladvantageous properties to the polymeric suds enhancers that increasetheir cleaning and/or suds boosting and/or suds retention properties.Further, such units may increase the interactions between the polymer,which is neutral or positively charged, and the soil which is negativelycharged.

[0070] Additionally, the polymeric suds enhancer can be present as thefree base or as a salt. Typical counter ions include, acetate, citrate,maleate, sulfate, chloride, etc.

[0071] Further, the polymeric suds enhancers of the present inventionmay be copolymers, terpolymers with random and/or repeating units,and/or block polymers such as di-, tri- and multi-block polymers.

[0072] For example a copolymer can be made from two monomers, G and H,such that G and H are randomly distributed in the copolymer, such as

GHGGHGGGGGHHG . . . etc.

[0073] or G and H can be in repeating distributions in the copolymer,for example

GHGHGHGHGHGHGH . . . etc.,

or

GGGGGHHGGGGGHH . . . etc.,

[0074] The same is true of the terpolymer, the distribution of the threemonomers can be either random or repeating.

[0075] The polymeric suds enhancers (suds boosters) of the presentinvention preferably have a molecular weight in the range of from about1,000 to about 2,000,000, preferably from about 5,000 to about1,000,000, more preferably from about 10,000 to about 750,000, morepreferably from about 10,000 to about 500,000, even more preferably fromabout 15,000 to about 300,000 daltons. Most preferably, the molecularweight of the polymeric suds enhancers is about 50,000 daltons or less.

[0076] The molecular weight of the polymeric suds enhancers of thepresent invention are determined using a Gel Filtration Chromatography(GFC) Method. Under this GFC Method, polymers are separated using GFCcolumns to determine molecular weight distribution. The molecular weightand distributions are measured through separation of the polymer speciesbased on their hydrodynamic volumes. The hydrodynamic volume is relatedto molecular weight.

[0077] A detailed example of how the molecular weights of the polymericsuds enhancers of the present invention are determined follows. A 0.2%solution of the polymeric suds enhancer is first prepared in the aqueousmobile phase, 80/20 0.5M Ammonium Acetate/Methanol at pH 3.7. Thesolution is then injected onto the GFC column at 60° C. and its absolutemolecular weight and molecular weight distribution are calculated usingboth multi-angle laser light scattering (MALLS) and refractive index(RI) detection. Theoretical and practical examples of molecular weightsdetermined by the GFC Method are found in: W. W. Yau, J. J. Kirkland,and D. D. Bly, Modern Size-Exclusion Liquid Chromatography, John Wiley &Sons, New York, 1979.

[0078] Quaternary Nitrogen-Containing Monomeric Units

[0079] Any suitable quaternary nitrogen-containing group can be used asa monomeric unit of the polymeric suds enhancers of the presentinvention.

[0080] Nonlimiting examples of quaternary nitrogen-containing monomericunits suitable for the polymeric suds enhancers of the present inventioninclude:

[0081] wherein R¹ is a hydrogen or a methyl group, preferably a methylgroup; R², R³ and R⁴ are linear or branched C₁-C₄ alkyl groups,preferably C₁ groups; n represents an integer from 1 to 4, preferably 3;and X⁻ represents a counterion which is compatible with thewater-soluble or water-dispersible nature of the polymer, preferablyCl⁻;

[0082] wherein R⁵, R⁶, R⁷ and R⁸ are independently H, or a C₁-C₄ alkylgroup, preferably a methyl group; k is an integer from 1 to 4,preferably 2; and X⁻ represents a counterion which is compatible withthe water-soluble or water-dispersible nature of the polymer, preferablyCl⁻; and

[0083] wherein R¹ and R² are independently H or a C₁-C₄ alkyl group,preferably a methyl group.

[0084] Zwitterionic Units

[0085] Any suitable zwitterionic group can be used as a monomeric unitof the suds enhancers of the present invention.

[0086] Nonlimiting examples of zwitterionic monomeric units suitable forthe suds enhancers of the present invention include:

[0087] wherein R⁹, R¹⁰ and R¹¹ are independently H, or a C₁-C₄ alkylgroup, preferably a methyl group; and m is an integer from 1 to 4,preferably 2.

[0088] Nonlimiting examples of zwitterionic monomeric units inaccordance with the present invention include:

[0089] Other Monomers

[0090] In addition to the quaternary nitrogen-containing monomeric unitsand/or the zwitterionic monomeric units, the suds enhancers of thepresent invention may, and preferably do include one or more othermonomeric units, other than quaternary nitrogen-containing monomericunits and zwitterionic monomeric units, such as amine oxide monomericunits, other cationic monomeric units, hydroxyl-containing monomericunits, hydrophobic monomeric units, hydrophilic monomeric units, anionicmonomeric units and nonionic monomeric units.

[0091] Amine Oxide Monomeric Units

[0092] The polymeric suds enhancers of the present invention maycomprise an amine oxide monomeric unit having the formula:

[0093] wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group ormixtures thereof containing from about 8 to about 22 carbon atoms; R⁴ isan alkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

[0094] A preferred class of amine oxide monomer units suitable for useas a polymeric suds volume and suds duration enhancer has the formula:

[0095] wherein X is either O or N, n is an integer from 1 to 10,preferably from 2 to 6, more preferably 2 to 4.

[0096] Cationic Monomeric Units

[0097] For the purposes of the present invention the term “cationicmonomeric unit” is defined as “a moiety which when incorporated into thestructure of the suds enhancers of the present invention, is capable ofmaintaining a cationic charge within the pH range of from about 4 toabout 12. The cationic monomeric unit is not required to be protonatedat every pH value within the range of about 4 to about 12.” Non-limitingexamples of monomeric units which comprise a cationic moiety, other thana quaternary nitrogen-containing moiety, include the cationic monomericunits having the formula:

[0098] wherein each of R¹, R² and R³ are independently selected from thegroup consisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof,preferably hydrogen, C₁ to C₃ alkyl, more preferably, hydrogen ormethyl. T is selected from the group consisting of substituted orunsubstituted, saturated or unsaturated, linear or branched radicalsselected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl,aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,alkoxy, keto, ester, ether, carbonyl, amido, amino, glycidyl, carbanato,carbamate, carboxylic, and carboalkoxy radicals and mixtures thereof. Zis selected from the group consisting of: —(CH₂)—, (CH₂—CH═CH)—,—(CH₂—CHOH)—, (CH₂—CHNR⁴)—, —(CH₂—CHR⁵—O)— and mixtures thereof,preferably —(CH₂)—. R⁴ and R⁵ are selected from the group consisting ofhydrogen, C₁ to C₆ alkyl and mixtures thereof, preferably hydrogen,methyl, ethyl and mixtures thereof; z is an integer selected from about0 to about 12, preferably about 2 to about 10, more preferably about 2to about 6. A is NR⁶R⁷ or NR⁶R⁷R⁸. Wherein each of R⁶, R⁷ and R⁸, whenpresent, are independently selected from the group consisting of H,C₁-C₈ linear or branched alkyl, alkyleneoxy having the formula:

—(R⁹O)_(y)R¹⁰

[0099] wherein R⁹ is C₂-C₄ linear or branched alkylene, and mixturesthereof, R¹⁰ is hydrogen, C₁-C₄ alkyl, and mixtures thereof, y is from 1to about 10. Preferably R⁶, R⁷ and R⁸, when present, are independently,hydrogen, C₁ to C₄ alkyl. Alternatively, NR⁶R⁷ or NR⁶R⁷R⁸ can form aheterocyclic ring containing from 4 to 7 carbon atoms, optionallycontaining additional hetero atoms, optionally fused to a benzene ring,and optionally substituted by C₁ to C₈ hydrocarbyl, and/or acetates.Examples of suitable heterocycles, both substituted and unsubstituted,are indolyl, isoindolinyl imidazolyl, imidazolinyl, piperidinylpyrazolyl, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl,pyrrolidinyl, guanidino, amidino, quinidinyl, thiazolinyl, morpholineand mixtures thereof, with morpholino and piperazinyl being preferred.

[0100] Examples of the cationic unit of formula [I] include, but are notlimited to, the following structures:

[0101] A preferred cationic monomeric unit is 2-dimethylaminoethylmethacrylate (DMAM) having the formula:

[0102] Nonlimiting examples of cationic monomeric units include: methylchloride quats of dimethylethyl(meth)acrylates, methyl chloride quats ofdimethylaminopropyl(meth)acrylamides, dimethyl- and diethylsulfate quatsof dimethylaminoethyl(meth)acrylates, dimethyl- and diethylsulfate quatsof dimethylaminopropyl(meth)acrylamides, and diallydimethylammoniumhalides, such as bromide and/or chloride salts.

[0103] Hydroxyl-Containing Monomeric Units

[0104] The hydroxyl group density of a quaternary nitrogen-containingmonomer- and/or zwitterionic monomer-containing polymeric suds enhancerof the present invention is determined by the following calculation.${{Hydroxyl}\quad {Group}\quad {Density}} = \frac{\left\lbrack {{Molecular}\quad {Weight}\quad {of}\quad {Hydroxyl}\quad {Group}} \right\rbrack}{\left\lbrack {{Total}\quad {Monomer}\quad {Molecular}\quad {Weight}} \right\rbrack}$

[0105] For example, the Hydroxyl Group Density of a quaternarynitrogen-containing monomer- and/or zwitterionic monomer-containingpolymeric suds enhancer containing 2-dimethylaminoethyl methacrylatehaving a molecular weight of approximately 157 and hydroxyethylacrylatehaving a molecular weight of approximately 116 grams/mole, at a 1:3 moleratio would be calculated as follows:${{Hydroxyl}\quad {Group}\quad {Density}} = {\frac{\lbrack 17\rbrack}{\left\lbrack {{3(116)} + 157} \right\rbrack} = 0.0337}$

[0106] Preferably, the quaternary nitrogen-containing or zwitterionicpolymeric suds enhancers of the present invention have a Hydroxyl GroupDensity of about 0.5 or less, preferably from about 0.0001 to about 0.4.

[0107] Nonlimiting examples of such hydroxyl group-containing unitsinclude, but are not limited to the following:

[0108] wherein n is an integer from 2 to 100, preferably 2 to 50, morepreferably 2 to 30,

[0109] Hydrophobic Group-Containing Monomeric Units

[0110] Suitable hydrophobic group-containing monomeric units for use inthe present invention include, but are not limited to, hydrophobicgroups preferably selected from the group consisting of non-hydroxylgroups, non-cationic groups, non-anionic groups, non-carbonyl groups,and/or non-H-bonding groups, more preferably selected from the groupconsisting of alkyls, cycloalkyls, aryls, alkaryls, aralkyls andmixtures thereof.

[0111] Nonlimiting examples of such hydrophobic group-containingmonomeric units include, but are not limited to the following:

[0112] Hydrophilic Group-Containing Monomeric Units

[0113] Suitable hydrophilic group-containing monomeric units for use inthe present invention include, but are not limited to, hydrophilicgroups preferably selected from the group consisting of carboxyl groups,carboxylic acids and their salts, sulfonic acids and their salts,heteroatom-containing moieties present in a ring or linear form andmixtures thereof.

[0114] Nonlimiting examples of such hydrophilic group-containingmonomeric units include, but are not limited to the following:

[0115] Anionic Monomeric Units

[0116] For the purposes of the present invention the term “anionicmonomeric unit” is defined as “a moiety which when incorporated into thestructure of the suds enhancers of the present invention, is capable ofmaintaining an anionic charge within the pH range of from about 4 toabout 12. The anionic monomeric unit is not required to be de-protonatedat every pH value within the range of about 4 to about 12.” Nonlimitingexamples of anionic monomeric units include: acrylic acid, methacrylicacid, AMPS, vinyl sulfonate, styrene vinyl sulfonate, vinyl phosphonicacid, ethylene glycol methacrylate phosphate, maleic anhydride and acid,fumaric acid, itaconic acid, glutamic acid, aspartic acid, the monomericunit having the formula:

[0117] and the monomeric unit having the formula:

[0118] the latter of which also comprises a moiety capable of having acationic charge at a pH of about 4 to about 12. This latter unit isdefined herein as “a unit capable of having an anionic and a cationiccharge at a pH of from about 4 to about 12.”

[0119] Nonionic Monomeric Units

[0120] For the purposes of the present invention the term “nonionicmonomeric unit” is defined as “a moiety which when incorporated into thestructure of the suds enhancers of the present invention, has no chargewithin the pH range of from about 4 to about 12.” Non-limiting examplesof units which are “nonionic monomeric units” are styrene, ethylene,propylene, butylene, 1,2-phenylene, esters, amides, ketones, ethers,acrylamide and the N-monosubstituted-(e.g., N-isopropylacrylamide) andN,N-disubstituted (e.g., N,N-dimethylacrylamide)acrylamides,hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, vinylpyrrolidone, alkyl substituted alkoxylated (meth)acrylate,dimethylaminoethyl(meth)acrylate, dimethylaminopropyl(meth)acrylamide,vinyl formamide and the like.

[0121] The units which comprise the polymers of the present inventionmay, as single units or monomers, have any pK_(a) value.

[0122] Preferably, the quaternary nitrogen-containing monomer- orzwitterionic monomer-containing polymeric suds enhancers are selectedfrom copolymers, which can optionally be crosslinked, terpolymers andother polymers (or multimers).

[0123] Particular Polymers

[0124] Preferred polymers of the present invention comprise:

[0125] A. at least one monomeric unit selected from the group consistingof:

[0126] (i) quaternary nitrogen-containing monomeric units having theformula:

[0127] wherein R¹ is a hydrogen or a methyl group, preferably a methylgroup; R², R³ and R⁴ are linear or branched C₁-C₄ alkyl groups,preferably C₁ groups; n represents an integer from 1 to 4, preferably 3;and X⁻ represents a counterion which is compatible with thewater-soluble or water-dispersible nature of the polymer, preferablyCl⁻; and

[0128] wherein R⁵, R⁶, R⁷ and R⁸ are independently H, or a C₁-C₄ alkylgroup, preferably a methyl group; k is an integer from 1 to 4,preferably 2; and X⁻ represents a counterion which is compatible withthe water-soluble or water-dispersible nature of the polymer, preferablyCl⁻;

[0129] (ii) zwitterionic monomeric units having the formula:

[0130] wherein R⁹, R¹⁰ and R¹¹ are independently H, or a C₁-C₄ alkylgroup, preferably a methyl group; and m is an integer from 1 to 4,preferably 2; and

[0131] (iii) mixtures thereof.

[0132] B. optionally, at least one cationic monomeric unit having aformula:

[0133]  wherein:

[0134] R¹ is H or an alkyl having 1 to 10 carbon atoms,

[0135] R² is a moiety selected from the group consisting of

[0136] wherein R³ is selected from the group consisting of

[0137] a is an integer from 0 to 16, preferably 0 to 10;

[0138] b is an integer from 2 to 10;

[0139] c is an integer from 2 to 10;

[0140] d is an integer from 1 to 100;

[0141] R⁴ and R⁵ are independently selected from the group consisting of—H, and

[0142] R⁸ is independently selected from the group consisting of a bondor an alkylene having 1 to 18 carbon atoms;

[0143] R⁹ and R¹⁰ are independently selected from the group consistingof —H, alkyl having 1 to 8 carbon atoms, and an olefin chain having 2 to8 carbon atoms;

[0144] R¹² and R¹³ are independently selected from the group consistingof H and alkyl having from 1 to 8 carbon atoms;

[0145] wherein x is an integer from 2 to 10;

[0146] C. optionally, at least one monomeric unit selected from thegroup consisting of:

[0147] a monomeric unit of the formula:

[0148]  wherein

[0149] R²⁰ is selected from the group consisting of H and CH₃;

[0150] R²¹ is selected from the group consisting of:

[0151] wherein e is an integer from 2 to 25, preferably from 2 to 5;

—O—(CH₂)_(f)—CH₃

[0152] wherein f is an integer from 0 to 25, preferably from 0 to 12;

[0153] wherein g is an integer from 1 to 100, preferably 1 to 50;

[0154] wherein h is an integer from 1 to 100, preferably 1 to 50;

[0155] R²³ is —H, —CH₃ or —C₂H₅;

[0156] R²⁴ is —CH₃ or —C₂H₅;

[0157] wherein R′ and R″ are independently H or CH₃; and j is an integerfrom 1 to 25, preferably 2 to 12;

[0158] wherein k is an integer from 1 to 25, preferably 1 to 12;

[0159] —NH—(CH₂)_(m)—NH₂.HCl, wherein m is an integer from 1 to 25,preferably 2 to 12; and

[0160] a polyhydroxy monomeric unit of formula:

[0161] wherein n is an integer from 1 to 50, preferably 1 to 25; and

[0162] D. optionally at least one monomeric unit selected from the groupconsisting of:

[0163] wherein R²⁵ is —H or —CH₃;

[0164] wherein R²⁶ is 13 H.

[0165] A preferred terpolymer and/or multimer of the present inventioncomprises at least one said monomeric unit A, at least one saidmonomeric unit B and at least one said monomeric unit C.

[0166] Preferably, at least one monomeric unit B is selected from thegroup consisting of:

[0167] wherein R³⁰ is H or —CH₃,

[0168] wherein R³¹ is a bond or

[0169] and

[0170] R³² and R³³ are —CH₃ or —C₂H₅.

[0171] Preferably, the polymer is a terpolymer in which:

[0172] said at least one monomeric unit C is selected from the groupconsisting of:

[0173]  wherein

[0174] R³⁸ is selected from the group consisting of H and CH₃ and

[0175] R⁴⁰ is selected from the group consisting of —CH₂CH₂—OH and

[0176] and isomers thereof; and

[0177] said terpolymer comprising said at least one monomeric unit D.

[0178] Preferably, the polymer has at least one monomeric unit C whichhas the formula:

[0179] wherein q ranges from 1 to 12, preferably 1 to 10, morepreferably 1 to 9.

[0180] Preferably, the polymer is a terpolymer, in which at least onemonomeric unit B is selected from the group consisting of:

[0181] wherein R¹⁰ is H or CH₃;

[0182] R¹¹ is a bond or

[0183] and R¹² and R¹³ are —CH₃ or —C₂H₅, and said polymer comprisessaid at least one monomeric unit D.

[0184] Preferably, at least one monomeric unit B has a formula selectedfrom the group consisting of:

[0185] Preferably, at least one monomeric unit B has a formula selectedfrom the group consisting of:

[0186] Preferably, at least one one monomeric unit C is selected fromthe group consisting of:

[0187] wherein n is an integer from 2 to 50, preferably 2 to 30, morepreferably 2 to 27;

[0188] Specific Polymers

[0189] Nonlimiting examples of such copolymers, which can optionally becrosslinked, terpolymers and multimers have the following formulas:

[0190] Examples of more preferred polymers of the present invention arethe following:

[0191] The liquid detergent compositions according to the presentinvention comprise at least an effective amount of the quaternarynitrogen-containing or zwitterionic polymeric suds enhancers describedherein, preferably from about 0.01% to about 10%, more preferably fromabout 0.001% to about 5%, most preferably from about 0.1% to about 2% byweight, of said composition. What is meant herein by “an effectiveamount quaternary nitrogen-containing or zwitterionic polymeric sudsenhancers” is that the suds volume and suds duration produced by thepresently described compositions are sustained for an increased amountof time relative to a composition which does not comprise one or more ofthe quaternary nitrogen-containing or zwitterionic polymeric sudsenhancer described herein. Additionally, the quaternarynitrogen-containing or zwitterionic polymeric suds enhancer can bepresent as the free base or as a salt. Typical counter ions include,acetate, citrate, maleate, sulfate, chloride, etc.

[0192] Proteinaceous Suds Enhancers

[0193] The proteinaceous suds enhancers of the present invention can bepeptides, polypeptides, amino acid containing copolymers, terpolymersetc., and mixtures thereof. Any suitable amino acid can be used to formthe backbone of the peptides, polypeptides, or amino acid, wherein thepolymers have an average cationic charge density of 2.8 or less,preferably from about 0.01 to about 2.8, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

[0194] In general, the amino acids suitable for use in forming theproteinaceous suds enhancers of the present invention have the formula:

[0195] wherein R and R¹ are each independently hydrogen, C₁-C₆ linear orbranched alkyl, C₁-C₆ substituted alkyl, and mixtures thereof.Non-limiting examples of suitable moieties for substitution on the C₁-C₆alkyl units include amino, hydroxy, carboxy, amido, thio, thioalkyl,phenyl, substituted phenyl, wherein said phenyl substitution is hydroxy,halogen, amino, carboxy, amido, and mixtures thereof. Furthernon-limiting examples of suitable moieties for substitution on the R andR¹ C₁-C₆ alkyl units include 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl,4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl,3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino,amidino, and mixtures thereof. Preferably R¹ is hydrogen and at least10% of R units are moieties which are capable of having a positive ornegative charge at a pH of from about 4 to about 12. Each R² isindependently hydrogen, hydroxy, amino, guanidino, C₁-C₄ alkyl, orcomprises a carbon chain which can be taken together with R, R¹ any R²units to form an aromatic or non-aromatic ring having from 5 to 10carbon atoms wherein said ring may be a single ring or two fused rings,each ring being aromatic, non-aromatic, or mixtures thereof. When theamino acids according to the present invention comprise one or morerings incorporated into the amino acid backbone, then R, R¹, and one ormore R² units will provide the necessary carbon-carbon bonds toaccommodate the formation of said ring. Preferably when R is hydrogen,R¹ is not hydrogen, and vice versa; preferably at least one R² ishydrogen. The indices x and y are each independently from 0 to 2.

[0196] An example of an amino acid according to the present inventionwhich contains a ring as part of the amino acid backbone is2-aminobenzoic acid (anthranilic acid) having the formula:

[0197] wherein x is equal to 1, y is equal to 0 and R, R¹, and 2 R²units from the same carbon atom are taken together to form a benzenering.

[0198] A further example of an amino acid according to the presentinvention which contains a ring as part of the amino acid backbone is3-aminobenzoic acid having the formula:

[0199] wherein x and y are each equal to 1, R is hydrogen and R¹ andfour R² units are taken together to form a benzene ring.

[0200] Non-limiting examples of amino acids suitable for use in theproteinaceous suds enhancers of the present invention wherein at leastone x or y is not equal to 0 include 2-aminobenzoic acid, 3-aminobenzoicacid, 4-aminobenzoic acid, b-alanine, and b-hydroxyaminobutyric acid.

[0201] The preferred amino acids suitable for use in the proteinaceoussuds enhancers of the present invention have the formula:

[0202] wherein R and R¹ are independently hydrogen or a moiety asdescribe herein above preferably R¹ is hydrogen and R comprise a moietyhaving a positive charge at a pH of from about 4 to about 12 wherein thepolymers have an average cationic charge density of 2.8 or less,preferably from about 0.01 to about 2.8, more preferably from about 0.1to about 2.75, most preferably from about 0.75 to about 2.25 units per100 daltons molecular weight at a pH of from about 4 to about 12.

[0203] More preferred amino acids which comprise the proteinaceous sudsenhancers of the present invention have the formula:

[0204] wherein R hydrogen, C₁-C₆ linear or branched alkyl, C₁-C₆substituted alkyl, and mixtures thereof. R is preferably C₁-C₆substituted alkyl wherein preferred moieties which are substituted onsaid C₁-C₆ alkyl units include amino, hydroxy, carboxy, amido, thio,C₁-C₄ thioalkyl, 3-imidazolyl, 4-imidazolyl, 2-imidazolinyl,4-imidazolinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,1-pyrazolyl, 3-pyrazoyl, 4-pyrazoyl, 5-pyrazoyl, 1-pyrazolinyl,3-pyrazolinyl, 4-pyrazolinyl, 5-pyrazolinyl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, piperazinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, guanidino,amidino, phenyl, substituted phenyl, wherein said phenyl substitution ishydroxy, halogen, amino, carboxy, and amido.

[0205] An example of a more preferred amino acid according to thepresent invention is the amino acid lysine having the formula:

[0206] wherein R is a substituted C₁ alkyl moiety, said substituent is4-imidazolyl.

[0207] Non-limiting examples of preferred amino acids include alanine,arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid,glycine, histidine, isoleucine, leucine, lysine, methionine,phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine,and mixtures thereof. The aforementioned amino acids are typicallyreferred to as the “primary a-amino aids”, however, the proteinaceoussuds enhancers of the present invention may comprise any amino acidhaving an R unit which together with the aforementioned amino acidsserves to adjust the cationic charge density of the proteinaceous sudsenhancers to a range of 2.8 or less, preferably from about 0.01 to about2.8, more preferably from about 0.1 to about 2.75, most preferably fromabout 0.75 to about 2.25 units per 100 daltons molecular weight at a pHof from about 4 to about 12. For example, further non-limiting examplesof amino acids include homoserine, hydroxyproline, norleucine,norvaline, ornithine, penicillamine, and phenylglycine, preferablyornithine. R units preferably comprise moieties which are capable of acationic or anionic charges within the range of pH from about 4 to about12. Non-limiting examples of preferred amino acids having anionic Runits include glutamic acid, aspartic acid, and g-carboxyglutamic acid.

[0208] For the purposes of the present invention, both optical isomersof any amino acid having a chiral center serve equally well forinclusion into the backbone of the peptide, polypeptide, or amino acidcopolymers. Racemic mixtures of one amino acid may be suitably combinedwith a single optical isomer of one or more other amino acids dependingupon the desired properties of the final proteinaceous suds enhancer.The same applies to amino acids capable of forming diasteriomeric pairs,for example, threonine.

[0209] Nonlimiting examples of suitable proteinaceous suds enhancers aredescribed in PCT Application Serial No. PCT/US98/24707.

[0210] Polyamino Acid Proteinaceous Suds enhancer—One type of suitableproteinaceous suds enhancer according to the present invention iscomprised entirely of the amino acids described herein above. Saidpolyamino acid compounds may be naturally occurring peptides,polypeptides, enzymes, and the like, provided that the polymers have anaverage cationic charge density of 2.8 or less, preferably from about0.01 to about 2.8, more preferably from about 0.1 to about 2.75, mostpreferably from about 0.75 to about 2.25 units per 100 daltons molecularweight at a pH of from about 4 to about 12. An example of a polyaminoacid which is suitable as a proteinaceous suds enhancer according to thepresent invention is the enzyme lysozyme.

[0211] An exception may, from time to time, occur in the case wherenaturally occurring enzymes, proteins, and peptides are chosen asproteinaceous suds enhancers provided that the polymers have an averagecationic charge density of 2.8 or less, preferably from about 0.01 toabout 2.8, more preferably from about 0.1 to about 2.75, most preferablyfrom about 0.75 to about 2.25 units per 100 daltons molecular weight ata pH of from about 4 to about 12.

[0212] Another class of suitable polyamino acid compound is thesynthetic peptide having a molecular weight of at least about 1500daltons. In addition, the polymers have an average cationic chargedensity of 2.8 or less, preferably from about 0.01 to about 2.8, morepreferably from about 0.1 to about 2.75, most preferably from about 0.75to about 2.25 units per 100 daltons molecular weight at a pH of fromabout 4 to about 12. An example of a polyamino acid synthetic peptidesuitable for use as a proteinaceous suds enhancer according to thepresent invention is the copolymer of the amino acids lysine, alanine,glutamic acid, and tyrosine having an average molecular weight of 52,000daltons and a ratio of lys:ala:glu:tyr of approximately 5:6:2:1.

[0213] Without wishing to be limited by theory, the presence of one ormore cationic amino acids, for example, histidine, ornithine, lysine andthe like, is required to insure increased suds stabilization and sudsvolume. However, the relative amount of cationic amino acid present, aswell as the average cationic charge density of the polyamino acid, arekey to the effectiveness of the resulting material. For example, polyL-lysine having a molecular weight of approximately 18,000 daltonscomprises 100% amino acids which have the capacity to possess a positivecharge in the pH range of from about 4 to about 12, with the result thatthis material is ineffective as a suds extender and as a greasy soilremoving agent.

[0214] Peptide Copolymers—Another class of materials suitable for use asproteinaceous suds enhancers according to the present invention arepeptide copolymers. For the purposes of the present invention “peptidecopolymers” are defined as “polymeric materials with a molecular weightgreater than or equal to about 1500 daltons wherein at least about 10%by weight of said polymeric material comprises one or more amino acids”.

[0215] Peptide copolymers suitable for use as proteinaceous sudsenhancers may include segments of polyethylene oxide which are linked tosegments of peptide or polypeptide to form a material which hasincreased suds retention as well as formulatability.

[0216] Nonlimiting examples of amino acid copolymer classes include thefollowing.

[0217] Polyalkyleneimine copolymers comprise random segments ofpolyalkyleneimine, preferably polyethyleneimine, together with segmentsof amino acid residues. For example, tetraethylenepentamine is reactedtogether with polyglutamic acid and polyalanine to form a copolymerhaving the formula:

[0218] wherein m is equal to 3, n is equal to 0, i is equal to 3, j isequal to 5, x is equal to 3, y is equal to 4, and z is equal to 7.

[0219] However, the formulator may substitute other polyamines forpolyalkyleneimines, for example, polyvinyl amines, or other suitablepolyamine which provides for a source of cationic charge at a pH of from4 to abut 12 and which results in a copolymer having an average cationiccharge density of 2.8 or less, preferably from about 0.01 to about 2.8,more preferably from about 0.1 to about 2.75, most preferably from about0.75 to about 2.25 units per 100 daltons molecular weight at a pH offrom about 4 to about 12.

[0220] The formulator may combine non-amine polymers with protonatableas well as non-protonatable amino acids. For example, acarboxylate-containing homo-polymer may be reacted with one or moreamino acids, for example, histidine and glycine, to form an amino acidcontaining amido copolymer having the formula:

[0221] wherein said copolymer has a molecular weight of at least 1500daltons and a ratio of x:y:z of approximately 2:3:6.

[0222] Zwitterionic Polymers

[0223] The quaternary nitrogen-containing or zwitterionic polymeric sudsenhancers of the present invention are homopolymers or copolymerswherein the monomers which comprise said homopolymers or copolymerscontain a moiety capable of being protonated at a pH of from about 4 toabout 12, or a moiety capable of being de-protonated at a pH of fromabout 4 to about 12, of a mixture of both types of moieties.

[0224] A preferred class of zwitterionic polymers suitable for use as asuds volume and suds duration enhancer has the formula:

[0225] wherein R is C₁-C₁₂ linear alkylene, C₁-C₁₂ branched alkylene,and mixtures thereof; preferably C₁-C₄ linear alkylene, C₃-C₄ branchedalkylene; more preferably methylene and 1,2-propylene. The index x isfrom 0 to 6; y is 0 or 1; z is 0 or 1.

[0226] The index n has the value such that the zwitterionic polymers ofthe present invention have an average molecular weight of from about1,000 to about 2,000,000 preferably from about 5,000 to about 1,000,000,more preferably from about 10,000 to about 750,000, more preferably fromabout 20,000 to about 500,000, even more preferably from about 35,000 toabout 300,000 daltons. The molecular weight of the quaternarynitrogen-containing or zwitterionic polymeric suds boosters, can bedetermined via conventional gel permeation chromatography.

[0227] Nonlimiting examples of suitable zwitterionic polymers aredescribed in PCT Application Serial No. PCT/US98/24699

[0228] Cationic Charge Density

[0229] For the purposes of the present invention the term “cationiccharge density” is defined as “the total number of units that areprotonated at a specific pH per 100 daltons mass of polymer, orotherwise stated, the total number of charges divided by the daltonmolecular weight of the monomer unit or polymer.”

[0230] For illustrative purposes only, a polypeptide comprising 10 unitsof the amino acid lysine has a molecular weight of approximately 1028daltons, wherein there are 11 —NH₂ units. If at a specific pH within therange of from about 4 to about 12, 2 of the —NH₂ units are protonated inthe form of —NH₃ ⁺, then the cationic charge density is 2 cationiccharge units÷by 1028 daltons molecular weight=approximately 0.2 units ofcationic charge per 100 daltons molecular weight. This would, therefore,have sufficient cationic charge to suffice the cationic charge densityof the present invention, but insufficient molecular weight to be asuitable suds enhancer.

[0231] Polymers have been shown to be effective for delivering sudsingbenefits in a hand dishwashing context, provided the polymer contains acationic moiety, either permanent via a quaternary nitrogen or temporaryvia protonation. Without being limited by theory, it is believed thatthe cationic charge must be sufficient to attract the polymer tonegatively charged soils but not so large as to cause negativeinteractions with available anionic surfactants.

[0232] The cationic charge density may be determined as follows, wherethe cationic charge density is defined as the amount of cationic chargeon a given polymer, either by permanent cationic groups or viaprotonated groups, as a weight percent of the total polymer at thedesired wash pH. For example, with the terpolymer,DMAM/hydroxyethylacrylate (HEA)/acrylic acid (AA) where the ratio ofmonomers is 1 mole of DMAM for 3 moles of HEA for 0.33 moles of AA, wehave experimentally determined the pK_(a), see hereinafter as to howpK_(a) is measured, of this polymer to be 8.2. Thus, if the wash pH is8.2, then half of the available nitrogens will be protonated (and countas cationic) and the other half will not be protonated (and not becounted in the “cationic charge density”). Thus, since the Nitrogen hasa molecular weight of approximately 14 grams/mole, the DMAM monomer hasa molecular weight of approximately 157 grams/mole, the HEA monomer hasa molecular weight of approximately 116 grams/mole, and the AA monomerhas a molecular weight of approximately 72 grams/mole, the cationiccharge density can be calculated as follows:

Cationic Charge Density=(14/157+116+116+116)*50%=0.0132 or 1.32%.

[0233] Thus, 1.32% of the polymer contains cationic charges. Otherwisestated, the cationic charge density is 1.32 per 100 daltons molecularweight.

[0234] As another example, one could make a copolymer of DMAM withhydroxyethylacrylate (HEA), where the ratio of monomers is 1 mole ofDMAM for 3 moles of HEA. The DMAM monomer has a molecular weight ofapproximately 157 and the HEA monomer has a molecular weight of 116grams/mole. In this case the pK_(a) has been measured to be 7.6. Thus,if the wash pH is 5.0, all of the available nitrogens will beprotonated. The cationic charge density is then calculated:

Cationic Charge Density=14/(157+116+116+116)*100%=0.0277, or 2.77%.

[0235] Thus, the cationic charge density is 2.77 per 100 daltonsmolecular weight. Notice that in this example, the minimum repeatingunit is considered 1 DMAM monomer plus 3 HEA monomers.

[0236] Alternatively, the cationic charge density can be determined asfollows: where the cationic charge density is defined as the totalnumber of charges divided by the dalton molecular weight of the polymerat the desired wash pH. It can be calculated from the following equation${{Cationic}\quad {Charge}\quad {Density}} = \frac{\sum\limits_{i}{n_{i}f_{i}C_{i}}}{\sum\limits_{j}m_{J}}$

[0237] where n_(i) is the number of charged unit. f_(i) is the fractionof unit being charged. In the case of protonated species (AH⁺), f_(i)can be calculated from the measured pH and pK_(a).$f_{({{AH} +})} = \frac{10^{{pKa} - {pH}}}{1 + 10^{{pKa} - {pH}}}$

[0238] In the case of deprotonated anionic species (A⁻)$f_{({A -})} = \frac{10^{{pH} - {pKa}}}{1 + 10^{{pH} - {pKa}}}$

[0239] C_(i) is the charge of the unit, m_(j) is the dalton molecularweight of the individual monomer units.

[0240] For example, with polyDMAM, we have experimentally determined thepKa, see hereinafter as to how pKa is measured, of this polymer to be7.7. Thus, if the wash pH is 7.7, then half of the available nitrogenswill be protonated (and count as cationic) f_((AH+))=0.5 and the otherhalf will not be protonated (and not be counted in the “cationic chargedensity”). Thus, since the DMAM monomer has a molecular weight ofapproximately 157 grams/mole, the cationic charge density can becalculated:

Cationic Charge Density=(1*0.5/157)=0.00318 or 0.318%.

[0241] Thus, at the wash pH of 7.7, polyDMAM has a cationic chargedensity of 0.318 charge per 100 dalton molecular weight. As anotherexample, one could make a copolymer of DMAM with DMA, where the ratio ofmonomers is 1 mole of DMAM for 3 moles of DMA. The DMA monomer has amolecular weight of 99 grams/mole. In this case the pK_(a) has beenmeasured to be 7.6. Thus, if the wash pH is 5.0, all of the availablenitrogens will be protonated. The cationic charge density is thencalculated:

Cationic Charge Density=1/(157+99+99+99)=0.0022, or 0.22%.

[0242] At the wash pH of 5.0, a copolymer of DMAM with DMA has a chargedensity of 0.22 charge per 100 dalton molecular weight. Notice that inthis example, the minimum repeating unit is considered 1 DMAM monomerplus 3 DMA monomers.

[0243] A key aspect of this calculation is the pKa measurement for anyprotonatable species which will result in a cationic charge on theheteroatom. Since the pKa is dependent on the polymer structure andvarious monomers present, this must be measure to determine thepercentage of protonatable sites to count as a function of the desiredwash pH. This is an easy exercise for one skilled in the art. Based onthis calculation, the percent of cationic charge is independent ofpolymer molecular weight.

[0244] The pKa of a polymeric suds booster is determined in thefollowing manner. Make at least 50 mls of a 5% polymer solution, such asa polymer prepared according to any of Examples 1 to 5 as describedhereinafter, in ultra pure water(i.e. no added salt). At 25° C., takeinitial pH of the 5% polymer solution with a pH meter and record when asteady reading is achieved. Maintain temperature throughout the test at25° C. with a water bath and stir continuously. Raise pH of 50 mls ofthe aqueous polymer solution to 12 using NaOH (12N, 12.5M). Titrate 5mls of 0.1N HCl into the polymer solution. Record pH when steady readingis achieved. Repeat steps 4 and 5 until pH is below 3. The pKa wasdetermined from a plot of pH vs. volume of titrant using the standardprocedure as disclosed in Quantitative Chemical Analysis, Daniel C.Harris, W.H. Freeman & Chapman, San Francisco, USA 1982.

[0245] It has been surprisingly found that when a polymeric suds boosterof the present invention is at its optimum charge density, then reducingthe molecular weight of the polymeric suds booster increases sudsingperformance even in the presence of composite and/or greasy soils.Accordingly, then the polymeric suds booster is at its optimum chargedensity, the molecular weight of the polymeric suds booster, asdetermined in the manner described hereinbefore, is preferably in therange of from about 1,000 to about 2,000,000, more preferably from about5,000 to about 500,000, even more preferably from about 10,000 to about100,000, most preferably from about 20,000 to about 50,000 daltons.

Methods of Use

[0246] The present invention relates to a method for providing increasedsuds volume and increased suds retention in suds-forming and/orfoam-forming compositions, such as liquid dishwashing compositions,personal care compositions (i.e., shampoos, hand washing compositions,body washing composition, hair removal compositions, etc.), laundrydetergent compositions, especially laundry bars and/or high sudsphosphate laundry compositions, hard surface cleaning compositions,agrochemical foaming compositions, oil-field foaming compositions and/orfire-firefighting foaming compositions.

Liquid Dishwashing Compositions

[0247] The liquid detergent compositions according to the presentinvention comprise at least an effective amount of one or morequaternary nitrogen-containing or zwitterionic polymeric suds enhancersdescribed herein, preferably from about 0.01% to about 10%, morepreferably from about 0.001% to about 5%, most preferably from about0.1% to about 2% by weight, of said composition and optionally, buttypically, the balance comprising one or more cleaning adjuncts.Nonlimiting examples of suitable cleaning adjuncts include surfactantsincluding diamines, amine oxides, betaines and/or sultaines, enzymes,builders, solvents such as water and/or other carriers, hydrotropes,calcium and/or magnesium ion-containing materials, pH agents, perfumes,chelants, soil release polymers, polymeric dispersants, polysaccharides,abrasives, bactericides, tarnish inhibitors, opacifiers, dyes, buffers,antifungal or mildew control agents, thickeners, processing aids, sudsboosters, brighteners, anti-corrosive aids, stabilizers, antioxidantsand other suitable adjuncts known by those of ordinary skill in the art.

[0248] The compositions of this invention can be used to form aqueouswashing solutions for use in hand dishwashing. Generally, an effectiveamount of such compositions is added to water to form such aqueouscleaning or soaking solutions. The aqueous solution so formed is thencontacted with the dishware, tableware, and cooking utensils.

[0249] An effective amount of the detergent compositions herein added towater to form aqueous cleaning solutions can comprise amounts sufficientto form from about 500 to 20,000 ppm of composition in aqueous solution.More preferably, from about 800 to 5,000 ppm of the detergentcompositions herein will be provided in aqueous cleaning liquor.

[0250] The liquid dishwashing compositions of the present invention alsoprovide a means for preventing the redeposition of grease, oils, anddirt, especially grease, from the hand washing solution onto dishware.This method comprises contacting an aqueous solution of the compositionsof the present invention with soiled dishware and washing said dishwarewith said aqueous solution.

[0251] An effective amount of the detergent compositions herein added towater to form aqueous cleaning solutions according to the method of thepresent invention comprises amounts sufficient to form from about 500 to20,000 ppm of composition in aqueous solution. More preferably, fromabout 800 to 2,500 ppm of the detergent compositions herein will beprovided in aqueous cleaning liquor.

[0252] The liquid detergent compositions of the present invention areeffective for preventing the redeposition of grease from the washsolution back onto the dishware during washing. One measure ofeffectiveness of the compositions of the present invention involvesredeposition tests. The following test and others of similar nature areused to evaluate the suitability of the formulas described herein.

[0253] A polyethylene 2 L graduated cylinder is filled to the 1 Lgraduation mark with an aqueous (water=7 grain) solution comprising fromabout 500 to about 20,000 ppm of a liquid detergent compositionaccording to the present invention. A synthetic greasy soil compositionis then added to the cylinder and the solution is agitated. After aperiod of time the solution is decanted from the graduated cylinder andthe interior walls of the graduated cylinder are rinsed with a suitablesolvent or combination of solvents to recover any re-deposited greasysoil. The solvent is removed and the weight of greasy soil which remainsin solution is determined by subtracting the amount of soil recoveredfrom the amount initially added to the aqueous solution.

[0254] Other re-deposition test include immersion of tableware,flatware, and the like and recovering any re-deposited soil.

[0255] The above test can be further modified to determine the increasedamount of suds volume and suds duration. The solution is first agitatedthen subsequently challenged with portions of greasy soil with agitationbetween each subsequent soil addition. The suds volume can be easilydetermined by using the vacant volume of the 2 L cylinder as a guide.

[0256] The present invention is further illustrated by the followingexamples of quaternary nitrogen-containing monomer and/or zwitterionicmonomer-containing polymeric suds enhancers (enhancing agents), providedthat no observations or other statements made therein should beconstrued to limit the invention, unless otherwise expressly indicatedin the claims appended hereto. All amounts, parts, percentages, andratios expressed in this specification, including the claims are byweight unless otherwise apparent in context.

SYNTHESIS EXAMPLES Example 1 Preparation of Poly(AM-co-AA-co-MAPTAC)(2:6:2) Terpolymer

[0257] To a one-litre reaction flask, add sequentially demineralizedwater, 687.1 g, acrylamide (52%), 53.8 g, acrylic acid, 85.1 g,diethylaminopropylmethacrylamde methylchloride quaternium salt, MAPTAC(50%), 173.8 g, and EDTA (40%), 0.2 g, then the resulting mixture isheated to 80° C. under gentle nitrogen purging. The pH of the monomerssolution is about 2.4. When the temperature reaches 80° C., sodiumpersulfate solution (1 g in 1 g demineralized water) is added all atonce. Polymerization starts within five minutes, and cooling is neededto control the exotherm at the desired temperature. Maintain thetemperature at 80°C. for two hours and during this time the batch isgetting viscous. Add a second portion of sodium persulfate solution (0.1g in 1 g demineralized water) at the end of the one-hour hold, the batchis then heated up to 90° C. and maintained at 90° C. for two hours. Coolthe batch to room temperature following the two hours at 90° C. Theconversion is higher than 99.9% and the viscosity at 25° C. is about42,500 cps at 20.5% solids, and the pH of the solution is about 2.5.

[0258] The above example is the synthesis of a terpolymer ofacrylamide:acrylic acid:MAPTAC of a molar ratio of 2:6:2. Many otherpolymers of various compositions can be synthesized according to theabove typical procedure or with few modifications such as reactiontemperature (60°-90° C.), amount of initiator, pH, and the ways ofintroducing the monomers to the reactor.

[0259] Examples of the neutral monomers include acrylamide and theN-monosubstituted-(e.g N-isopropylacrylamide) and N,N-disubstituted(N,N-dimethylacrylamide)acrylamides, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, vinyl pyrrolidone, alkyl substitutredalkoxylated (meth)acrylate, dimethylaminoethyl(meth)acrylate,dimethylaminopropyl(meth)acrylamide, and vinyl formamide.

[0260] Examples of anionic monomers are acrylic acid, methacrylic acid,AMPS, vinyl sulfonate, styrene vinyl sulfonate, vinyl phosphonic acid,ethylene glycol methacrylate phosphate, maleic anhydride and acid,furmaic acid, and itaconic acid.

[0261] Cationic monomers are methyl chloride quats ofdimethylethyl(meth)acrylates, methyl chloride quats ofdimethylaminopropyl(meth)acrylamides, dimethyl-and diethylsulfate quatsof dimethylaminoethyl(meth)acrylates, dimethyl-and diethylsulfate quatsof dimethyaminopropyl(meth)acrylamides, and diallydimethylammoniumhalides (such as bromide and chloride salts).

FORMULATION EXAMPLES

[0262] In the following examples, the suds boosting polymer can be anyof the suds boosting polymers described herein, preferably one of thesuds boosting polymers according to Synthesis Examples 1-2 above.

Example 1

[0263] A liquid dishwasing composition according to the presentinvention is formulated as follows: INGREDIENTS (weight %) #1 #2 #3Surfactant Alkyl ethoxy sulfate 27.0 27.0 27.0 Amine oxide 6.5 6.5 6.5Alcohol ethoxylate 3.0 3.0 3.0 Diamine Technology Diamine 0.50 0.50 0.50Suds Boosting Polymer Technology Suds Boosting Compound 0.5 1.0 2.0Buffers/Alkalinity NaOH to pH to pH to pH Solvent/Hydrotropes/SaltsEthanol 6.5 5.0 8.0 Propylene Glycol 1.5 2.5 0.5 NaCl 0.8 0 0.1 SodiumCumene Sulfonate 3.0 4.5 1.5 Poly Propylene Glycol (Mw 2000 or 2600) 03.0 2.0 Perfume Perfume 0.36 0.36 0.36 pH (10% pc) 8.9 8.7 8.5

Example 2

[0264] A liquid dishwasing composition according to the presentinvention is formulated as follows: INGREDIENTS (weight %) SurfactantNaAE0.6S 27.0 27.0 C12/14 dimethyl amine oxide 6.5 6.5 C11E9 3.0 3.0Total Surfactant 36.5 36.5 Diamine Technology 1,3 BAC diamine 0.50 0.50New Suds Boosting Polymer Technology 2:6:2 Acryl Amide : Acrylic Acid:1.5 1.0 Methacrylamide Amido Propyl Trimethyl Ammonimum Chloride Mw 700K 3:1 Hydroxy Propyl Acrylate:DMAM-Mw — 0.5 265K Buffers/Alkalinity NaOHadjusted adjusted Solvent/Hydrotropes/Salts Ethanol 6.5 (5.0-8.0) 6.5(5.0-8.0) Propylene Glycol 0.5 (0.5-2.5) 0.5 (0.5-2.5) NaCl 0.9(0-1.0)   0.9 (0-1.0)   Sodium Cumene Sulfonate 2.5 (1.5-4.5) 2.5(1.5-4.5) Poly Propylene Glycol (Mw 2000 or 2600) 2.0 (0-3.0)   2.0(0-3.0)   Perfume 0.36 0.36 Viscosity (cps) 330 330 pH (10% pc) 8.5 8.5

[0265] While particular embodiments of the subject invention have beendescribed, it will be obvious to those skilled in the art that variouschanges and modifications of the subject invention can be made withoutdeparting from the spirit and scope of the invention. It is intended tocover, in the appended claims, all such modifications that are withinthe scope of the invention.

[0266] The compositions of the present invention can be suitablyprepared by any process chosen by the formulator, non-limiting examplesof which are described in U.S. Pat. No. 5,691,297 Nassano et al., issuedNov. 11, 1997; U.S. Pat. No. 5,574,005 Welch et al., issued Nov. 12,1996; U.S. Pat. No. 5,569,645 Dinniwell et al., issued Oct. 29, 1996;U.S. Pat. No. 5,565,422 Del Greco et al., issued Oct. 15, 1996; U.S.Pat. No. 5,516,448 Capeci et al., issued May 14, 1996; U.S. Pat. No.5,489,392 Capeci et al., issued Feb. 6, 1996; U.S. Pat. No. 5,486,303Capeci et al., issued Jan. 23, 1996 all of which are incorporated hereinby reference.

[0267] In addition to the above examples, the cleaning compositions ofthe present invention can be formulated into any suitable laundrydetergent composition, non-limiting examples of which are described inU.S. Pat. No. 5,679,630 Baeck et al., issued Oct. 21, 1997; U.S. Pat.No. 5,565,145 Watson et al., issued Oct. 15, 1996; U.S. Pat. No.5,478,489 Fredj et al., issued Dec. 26, 1995; U.S. Pat. No. 5,470,507Fredj et al., issued Nov. 28, 1995; U.S. Pat. No. 5,466,802 Panandikeret al., issued Nov. 14, 1995; U.S. Pat. No. 5,460,752 Fredj et al.,issued Oct. 24, 1995; U.S. Pat. No. 5,458,810 Fredj et al., issued Oct.17, 1995; U.S. Pat. No. 5,458,809 Fredj et al., issued Oct. 17, 1995;U.S. Pat. No. 5,288,431 Huber et al., issued Feb. 22, 1994 all of whichare incorporated herein by reference.

[0268] Having described the invention in detail with reference topreferred embodiments and the examples, it will be clear to thoseskilled in the art that various changes and modifications may be madewithout departing from the scope of the invention and the invention isnot to be considered limited to what is described in the specification.

What is claimed is:
 1. A liquid detergent composition having increasedsuds volume and suds retention suitable for use in hand dishwashing,said compositions comprising: a) an effective amount of a quaternarynitrogen-containing monomeric unit or zwitterionic monomericunit-containing polymeric suds enhancer, said enhancer comprising: i)units selected from the group consisting of units having the formula:

wherein R¹ is a hydrogen or a methyl group; R², R³ and R⁴ are linear orbranched C₁-C₄ alkyl groups; n represents an integer from 1 to 4; and X⁻represents a counterion which is compatible with the water-soluble orwater-dispersible nature of the polymer;

wherein R⁵, R⁶, R⁷ and R⁸ are independently H, or a C₁-C₄ alkyl group,preferably a methyl group; k is an integer from 1 to 4, preferably 2;and X⁻ represents a counterion which is compatible with thewater-soluble or water-dispersible nature of the polymer, preferablyCl⁻; and

wherein R¹ and R² are independently H or a C₁-C₄ alkyl group;

wherein R⁹ and R¹⁰ are independently H, or a C₁-C₄ alkyl group; and m isan integer from 1 to 4; and mixtures thereof; provided that said sudsenhancer has an average cationic charge density of 2.8 or less units per100 daltons molecular weight at a pH of from about 4 to about 12; b) aneffective amount of a detersive surfactant; and c) the balance carriersand other adjunct ingredients; provided that a 10% aqueous solution ofsaid detergent composition has a pH of from about 4 to about
 12. 2. Thecomposition according to claim 1 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer (a) furthercomprises: ii) one or more units having one or more hydroxyl groups,provided that said suds enhancer has a hydroxyl group density of 0.5 orless.
 3. The composition according to claim 1 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer (a) furthercomprises: iii) one or more units having one or more hydrophobic groupsselected from the group consisting of non-hydroxyl groups, non-cationicgroups, non-anionic groups, non-carbonyl groups, and/or non-H-bondinggroups.
 4. The composition according to claim 1 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer has anaverage cationic charge density of from about 0.01 to about 2.8 unitsper 100 daltons molecular weight at a pH of from about 4 to about
 12. 5.The composition according to claim 4 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer has anaverage cationic charge density of from about 0.1 to about 2.75 unitsper 100 daltons molecular weight at a pH of from about 4 to about
 12. 6.The composition according to claim 5 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer has anaverage cationic charge density of from 0.75 to about 2.25 units per 100daltons molecular weight at a pH of from about 4 to about
 12. 7. Thecomposition according to claim 2 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer has ahydroxyl group density of from about 0.0001 to about 0.4.
 8. Thecomposition according to claim 1 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer (a) furthercomprises a hydrophilic group-containing unit.
 9. The compositionaccording to claim 1 wherein said quaternary nitrogen-containing orzwitterionic polymeric suds enhancer (a) further comprises an anionicunit.
 10. The composition according to claim 1 wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer (a) furthercomprises: iv) units capable of having an anionic charge at a pH of fromabout 4 to about 12; v) units capable of having an anionic charge and acationic charge at a pH of from about 4 to about 12; vi) units having nocharge at a pH of from about 4 to about 12; and vii) mixtures of units(iv), (v), (vi), and (vii).
 11. The composition according to claim 1wherein said quaternary nitrogen-containing or zwitterionic polymericsuds stabilizer has an average molecular weight of from about 1,000 toabout 2,000,000 daltons.
 12. The composition according to claim 1further comprising from about 0.25% to about 15% of a diamine havingmolecular weight less than or equal to 400 g/mol.
 13. The compositionaccording to claim 12 wherein said diamine is1,3-bis(methylamine)-cyclohexane.
 14. The composition according to claim12 wherein said diamine has the formula:

wherein each R²⁰ is independently selected from the group consisting ofhydrogen, C₁-C₄ linear or branched alkyl, alkyleneoxy having theformula: —(R²¹O)_(y)R²² wherein R²¹ is C₂-C₄ linear or branchedalkylene, and mixtures thereof; R²² is hydrogen, C₁-C₄ alkyl, andmixtures thereof; y is from 1 to about 10; X is a unit selected from: i)C₃-C₁₀ linear alkylene, C₃-C₁₀ branched alkylene, C₃-C₁₀ cyclicalkylene, C₃-C₁₀ branched cyclic alkylene, an alkyleneoxyalkylene havingthe formula: —(R²¹O)_(y)R²¹—wherein R²¹ and y are the same as definedherein above; ii) C₃-C₁₀ linear, C₃-C₁₀ branched linear, C₃-C₁₀ cyclic,C₃-C₁₀ branched cyclic alkylene, C₆-C₁₀ arylene, wherein said unitcomprises one or more electron donating or electron withdrawing moietieswhich provide said diamine with a pK_(a) greater than about 8; and iii)mixtures of (i) and (ii) provided said diamine has a pK_(a) of at leastabout
 8. 15. The composition according to claim 14 wherein each R²⁰ ishydrogen and X is C₃-C₆ linear alkylene, C₃-C₆ branched alkylene, andmixtures thereof.
 16. The composition according to claim 1 wherein thedetersive surfactant (b) is selected from the group consisting of linearalkyl benzene sulfonates, a-olefin sulfonates, paraffin sulfonates,methyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, alkylsulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates,sarcosinates, taurinates, and mixtures thereof.
 17. The compositionaccording to claim 1, wherein said other adjuncts ingredients (c) isselected from the group consisting of: soil release polymers, polymericdispersants, polysaccharides, abrasives, bactericides, tarnishinhibitors, builders, enzymes, opacifiers, dyes, perfumes, thickeners,antioxidants, processing aids, suds boosters, buffers, antifungal ormildew control agents, insect repellants, anti-corrosive aids, chelantsand mixtures thereof.
 18. The composition according to claim 1, whereinsaid detersive surfactant (b) is selected from the group consisting ofamine oxides, polyhydroxy fatty acid amides, betaines, sulfobetaines,alkyl polyglycosides, alkyl ethoxylates, and mixtures thereof.
 19. Thecomposition according to claim 1, wherein said quaternarynitrogen-containing or zwitterionic polymeric suds stabilizer (a) is aproteinaceous suds enhancer.
 20. The composition according to claim 1,further comprising an enzyme selected from the group consisting ofprotease, amylase, and mixtures thereof.
 21. The composition accordingto claim 1, wherein said quaternary nitrogen-containing or zwitterionicpolymeric suds stabilizer comprises a cationic unit of the formula:

wherein each of R¹, R² and R³ are independently selected from the groupconsisting of hydrogen, C₁ to C₆ alkyl, and mixtures thereof; T isselected from the group consisting of substituted or unsubstituted,saturated or unsaturated, linear or branched radicals selected from thegroup consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl,heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,ester, ether, carbonyl, amido, amino, glycidyl, carbanato, carbamate,carboxylic, and carboalkoxy radicals and mixtures thereof; Z is selectedfrom the group consisting of: —(CH₂)—, (CH₂—CH═CH)—, —(CH₂—CHOH)—,(CH₂—CHNR⁴)—, —(CH₂—CHR⁵—O)— and mixtures thereof; R⁴ and R⁵ areselected from the group consisting of hydrogen, C₁ to C₆ alkyl andmixtures thereof; z is an integer selected from about 0 to about 12; Ais NR⁶R⁷ or NR⁶R⁷R⁸ wherein each of R⁶, R⁷ and R⁸, when present, areindependently selected from the group consisting of H, C₁-C₈ linear orbranched alkyl, alkyleneoxy having the formula: —(R⁹O)_(y)R¹⁰ wherein R⁹is C₂-C₄ linear or branched alkylene, and mixtures thereof; R¹⁰ ishydrogen, C₁-C₄ alkyl, and mixtures thereof; and y is from 1 to about10.
 22. The composition according to claim 21, wherein said quaternarynitrogen-containing or zwitterionic polymeric suds enhancer (a)comprises a cationic unit of the formula selected from the groupconsisting of:


23. A method for providing extended suds volume and suds duration whendishware in need of cleaning is washed, comprising the step ofcontacting said dishware with an aqueous solution of a liquid detergentcomprising: a) an effective amount of a quaternary nitrogen-containingor zwitterionic polymeric suds enhancer, said stabilizer comprising: i)units capable of having a cationic charge at a pH of from about 4 toabout 12; provided that said suds enhancer has an average cationiccharge density of 0.0275 or less units per 100 daltons molecular weightat a pH of from about 4 to about 12; b) an effective amount of adetersive surfactant; and c) the balance carriers and other adjunctingredients; provided that a 10% aqueous solution of said detergentcomposition has a pH of from about 4 to about 12.